cantera/Cantera/src/equil/vcs_elem.cpp
2008-08-18 23:17:18 +00:00

603 lines
18 KiB
C++

/**
* @file vcs_elem.cpp
* This file contains the algorithm for checking the satisfaction of the
* element abundances constraints and the algorithm for fixing violations
* of the element abundances constraints.
*/
/*
* $Id$
*/
#include "vcs_solve.h"
#include "vcs_internal.h"
#include "math.h"
namespace VCSnonideal {
//! Computes the current elemental abundances vector
/*!
* Computes the elemental abundances vector, m_elemAbundances[], and stores it
* back into the global structure
*/
void VCS_SOLVE::vcs_elab() {
for (int j = 0; j < m_numElemConstraints; ++j) {
m_elemAbundances[j] = 0.0;
for (int i = 0; i < m_numSpeciesTot; ++i) {
if (m_speciesUnknownType[i] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
m_elemAbundances[j] += m_formulaMatrix[j][i] * m_molNumSpecies_old[i];
}
}
}
}
/*
*
* vcs_elabcheck:
*
* This function checks to see if the element abundances are in
* compliance. If they are, then TRUE is returned. If not,
* FALSE is returned. Note the number of constraints checked is
* usually equal to the number of components in the problem. This
* routine can check satisfaction of all of the constraints in the
* problem, which is equal to ne. However, the solver can't fix
* breakage of constraints above nc, because that nc is the
* range space by definition. Satisfaction of extra constraints would
* have had to occur in the problem specification.
*
* The constraints should be broken up into 2 sections. If
* a constraint involves a formula matrix with positive and
* negative signs, and eaSet = 0.0, then you can't expect that the
* sum will be zero. There may be roundoff that inhibits this.
* However, if the formula matrix is all of one sign, then
* this requires that all species with nonzero entries in the
* formula matrix be identically zero. We put this into
* the logic below.
*
* Input
* -------
* ibound = 1 : Checks constraints up to the number of elements
* 0 : Checks constraints up to the number of components.
*
*/
int VCS_SOLVE::vcs_elabcheck(int ibound) {
int i;
int top = m_numComponents;
double eval, scale;
int numNonZero;
bool multisign = false;
if (ibound) {
top = m_numElemConstraints;
}
/*
* Require 12 digits of accuracy on non-zero constraints.
*/
for (i = 0; i < top; ++i) {
if (m_elementActive[i]) {
if (fabs(m_elemAbundances[i] - m_elemAbundancesGoal[i]) > (fabs(m_elemAbundancesGoal[i]) * 1.0e-12)) {
/*
* This logic is for charge neutrality condition
*/
if (m_elType[i] == VCS_ELEM_TYPE_CHARGENEUTRALITY) {
AssertThrowVCS(m_elemAbundancesGoal[i] == 0.0, "vcs_elabcheck");
}
if (m_elemAbundancesGoal[i] == 0.0 || (m_elType[i] == VCS_ELEM_TYPE_ELECTRONCHARGE)) {
scale = VCS_DELETE_MINORSPECIES_CUTOFF;
/*
* Find out if the constraint is a multisign constraint.
* If it is, then we have to worry about roundoff error
* in the addition of terms. We are limited to 13
* digits of finite arithmetic accuracy.
*/
numNonZero = 0;
multisign = false;
for (int kspec = 0; kspec < m_numSpeciesTot; kspec++) {
eval = m_formulaMatrix[i][kspec];
if (eval < 0.0) {
multisign = true;
}
if (eval != 0.0) {
scale = MAX(scale, fabs(eval * m_molNumSpecies_old[kspec]));
numNonZero++;
}
}
if (multisign) {
if (fabs(m_elemAbundances[i] - m_elemAbundancesGoal[i]) > 1e-11 * scale) {
return FALSE;
}
} else {
if (fabs(m_elemAbundances[i] - m_elemAbundancesGoal[i]) > VCS_DELETE_MINORSPECIES_CUTOFF) {
return FALSE;
}
}
} else {
/*
* For normal element balances, we require absolute compliance
* even for rediculously small numbers.
*/
if (m_elType[i] == VCS_ELEM_TYPE_ABSPOS) {
return FALSE;
} else {
return FALSE;
}
}
}
}
}
return TRUE;
} /* vcs_elabcheck() *********************************************************/
/*****************************************************************************/
/*****************************************************************************/
/*****************************************************************************/
void VCS_SOLVE::vcs_elabPhase(int iphase, double * const elemAbundPhase)
/*************************************************************************
*
* vcs_elabPhase:
*
* Computes the elemental abundances vector for a single phase,
* elemAbundPhase[], and returns it through the argument list.
* The mole numbers of species are taken from the current value
* in m_molNumSpecies_old[].
*************************************************************************/
{
int i, j;
for (j = 0; j < m_numElemConstraints; ++j) {
elemAbundPhase[j] = 0.0;
for (i = 0; i < m_numSpeciesTot; ++i) {
if (m_speciesUnknownType[i] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
if (m_phaseID[i] == iphase) {
elemAbundPhase[j] += m_formulaMatrix[j][i] * m_molNumSpecies_old[i];
}
}
}
}
}
/*****************************************************************************/
/*****************************************************************************/
/*****************************************************************************/
int VCS_SOLVE::vcs_elcorr(double aa[], double x[])
/**************************************************************************
*
* vcs_elcorr:
*
* This subroutine corrects for element abundances. At the end of the
* surbroutine, the total moles in all phases are recalculated again,
* because we have changed the number of moles in this routine.
*
* Input
* -> temporary work vectors:
* aa[ne*ne]
* x[ne]
*
* Return Values:
* 0 = Nothing of significance happened,
* Element abundances were and still are good.
* 1 = The solution changed significantly;
* The element abundances are now good.
* 2 = The solution changed significantly,
* The element abundances are still bad.
* 3 = The solution changed significantly,
* The element abundances are still bad and a component
* species got zeroed out.
*
* Internal data to be worked on::
*
* ga Current element abundances
* m_elemAbundancesGoal Required elemental abundances
* m_molNumSpecies_old Current mole number of species.
* m_formulaMatrix[][] Formular matrix of the species
* ne Number of elements
* nc Number of components.
*
* NOTES:
* This routine is turning out to be very problematic. There are
* lots of special cases and problems with zeroing out species.
*
* Still need to check out when we do loops over nc vs. ne.
*
*************************************************************************/
{
int i, j, retn = 0, kspec, goodSpec, its;
double xx, par, saveDir, dir;
#ifdef DEBUG_MODE
double l2before = 0.0, l2after = 0.0;
std::vector<double> ga_save(m_numElemConstraints, 0.0);
vcs_dcopy(VCS_DATA_PTR(ga_save), VCS_DATA_PTR(m_elemAbundances), m_numElemConstraints);
if (m_debug_print_lvl >= 2) {
plogf(" --- vcsc_elcorr: Element abundances correction routine");
if (m_numElemConstraints != m_numComponents) {
plogf(" (m_numComponents != m_numElemConstraints)");
}
plogf("\n");
}
for (i = 0; i < m_numElemConstraints; ++i) {
x[i] = m_elemAbundances[i] - m_elemAbundancesGoal[i];
}
l2before = 0.0;
for (i = 0; i < m_numElemConstraints; ++i) {
l2before += x[i] * x[i];
}
l2before = sqrt(l2before/m_numElemConstraints);
#endif
/*
* Special section to take out single species, single component,
* moles. These are species which have non-zero entries in the
* formula matrix, and no other species have zero values either.
*
*/
int numNonZero = 0;
bool changed = false;
bool multisign = false;
for (i = 0; i < m_numElemConstraints; ++i) {
numNonZero = 0;
multisign = false;
for (kspec = 0; kspec < m_numSpeciesTot; kspec++) {
if (m_speciesUnknownType[kspec] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
double eval = m_formulaMatrix[i][kspec];
if (eval < 0.0) {
multisign = true;
}
if (eval != 0.0) {
numNonZero++;
}
}
}
if (!multisign) {
if (numNonZero < 2) {
for (kspec = 0; kspec < m_numSpeciesTot; kspec++) {
if (m_speciesUnknownType[kspec] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
double eval = m_formulaMatrix[i][kspec];
if (eval > 0.0) {
m_molNumSpecies_old[kspec] = m_elemAbundancesGoal[i] / eval;
changed = true;
}
}
}
} else {
int numCompNonZero = 0;
int compID = -1;
for (kspec = 0; kspec < m_numComponents; kspec++) {
if (m_speciesUnknownType[kspec] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
double eval = m_formulaMatrix[i][kspec];
if (eval > 0.0) {
compID = kspec;
numCompNonZero++;
}
}
}
if (numCompNonZero == 1) {
double diff = m_elemAbundancesGoal[i];
for (kspec = m_numComponents; kspec < m_numSpeciesTot; kspec++) {
if (m_speciesUnknownType[kspec] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
double eval = m_formulaMatrix[i][kspec];
diff -= eval * m_molNumSpecies_old[kspec];
}
m_molNumSpecies_old[compID] = MAX(0.0,diff/m_formulaMatrix[i][compID]);
changed = true;
}
}
}
}
}
if (changed) {
vcs_elab();
}
/*
* Section to check for maximum bounds errors on all species
* due to elements.
* This may only be tried on element types which are VCS_ELEM_TYPE_ABSPOS.
* This is because no other species may have a negative number of these.
*
* Note, also we can do this over ne, the number of elements, not just
* the number of components.
*/
changed = false;
for (i = 0; i < m_numElemConstraints; ++i) {
int elType = m_elType[i];
if (elType == VCS_ELEM_TYPE_ABSPOS) {
for (kspec = 0; kspec < m_numSpeciesTot; kspec++) {
int irxn = kspec - m_numComponents;
if (m_speciesUnknownType[kspec] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
double atomComp = m_formulaMatrix[i][kspec];
if (atomComp > 0.0) {
double maxPermissible = m_elemAbundancesGoal[i] / atomComp;
if (m_molNumSpecies_old[kspec] > maxPermissible) {
#ifdef DEBUG_MODE
if (m_debug_print_lvl >= 3) {
plogf(" --- vcs_elcorr: Reduced species %s from %g to %g "
"due to %s max bounds constraint\n",
m_speciesName[kspec].c_str(), m_molNumSpecies_old[kspec],
maxPermissible, m_elementName[i].c_str());
}
#endif
m_molNumSpecies_old[kspec] = maxPermissible;
changed = true;
if (m_molNumSpecies_old[kspec] < VCS_DELETE_MINORSPECIES_CUTOFF) {
m_molNumSpecies_old[kspec] = 0.0;
if (m_SSPhase[kspec]) {
m_rxnStatus[kspec] = VCS_SPECIES_ZEROEDSS;
} else {
m_rxnStatus[kspec] = VCS_SPECIES_ZEROEDMS;
}
#ifdef DEBUG_MODE
if (m_debug_print_lvl >= 2) {
plogf(" --- vcs_elcorr: Zeroed species %s and changed "
"status to %d due to max bounds constraint\n",
m_speciesName[kspec].c_str(), m_rxnStatus[irxn]);
}
#endif
}
}
}
}
}
}
}
// Recalculate the element abundances if something has changed.
if (changed) {
vcs_elab();
}
/*
* Ok, do the general case. Linear algebra problem is
* of length nc, not ne, as there may be degenerate rows when
* nc .ne. ne.
*/
for (i = 0; i < m_numComponents; ++i) {
x[i] = m_elemAbundances[i] - m_elemAbundancesGoal[i];
if (fabs(x[i]) > 1.0E-13) retn = 1;
for (j = 0; j < m_numComponents; ++j) {
aa[j + i*m_numElemConstraints] = m_formulaMatrix[j][i];
}
}
i = vcsUtil_mlequ(aa, m_numElemConstraints, m_numComponents, x, 1);
if (i == 1) {
plogf("vcs_elcorr ERROR: mlequ returned error condition\n");
return VCS_FAILED_CONVERGENCE;
}
/*
* Now apply the new direction without creating negative species.
*/
par = 0.5;
for (i = 0; i < m_numComponents; ++i) {
if (m_molNumSpecies_old[i] > 0.0) {
xx = -x[i] / m_molNumSpecies_old[i];
if (par < xx) par = xx;
}
}
if (par > 100.0) {
par = 100.0;
}
par = 1.0 / par;
if (par < 1.0 && par > 0.0) {
retn = 2;
par *= 0.9999;
for (i = 0; i < m_numComponents; ++i) {
double tmp = m_molNumSpecies_old[i] + par * x[i];
if (tmp > 0.0) {
m_molNumSpecies_old[i] = tmp;
} else {
if (m_SSPhase[i]) {
m_molNumSpecies_old[i] = 0.0;
} else {
m_molNumSpecies_old[i] = m_molNumSpecies_old[i] * 0.0001;
}
}
}
} else {
for (i = 0; i < m_numComponents; ++i) {
double tmp = m_molNumSpecies_old[i] + x[i];
if (tmp > 0.0) {
m_molNumSpecies_old[i] = tmp;
} else {
if (m_SSPhase[i]) {
m_molNumSpecies_old[i] = 0.0;
} else {
m_molNumSpecies_old[i] = m_molNumSpecies_old[i] * 0.0001;
}
}
}
}
/*
* We have changed the element abundances. Calculate them again
*/
vcs_elab();
/*
* We have changed the total moles in each phase. Calculate them again
*/
vcs_tmoles();
/*
* Try some ad hoc procedures for fixing the problem
*/
if (retn >= 2) {
/*
* First find a species whose adjustment is a win-win
* situation.
*/
for (kspec = 0; kspec < m_numSpeciesTot; kspec++) {
if (m_speciesUnknownType[kspec] == VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
continue;
}
saveDir = 0.0;
goodSpec = TRUE;
for (i = 0; i < m_numComponents; ++i) {
dir = m_formulaMatrix[i][kspec] * (m_elemAbundancesGoal[i] - m_elemAbundances[i]);
if (fabs(dir) > 1.0E-10) {
if (dir > 0.0) {
if (saveDir < 0.0) {
goodSpec = FALSE;
break;
}
} else {
if (saveDir > 0.0) {
goodSpec = FALSE;
break;
}
}
saveDir = dir;
} else {
if (m_formulaMatrix[i][kspec] != 0.) {
goodSpec = FALSE;
break;
}
}
}
if (goodSpec) {
its = 0;
xx = 0.0;
for (i = 0; i < m_numComponents; ++i) {
if (m_formulaMatrix[i][kspec] != 0.0) {
xx += (m_elemAbundancesGoal[i] - m_elemAbundances[i]) / m_formulaMatrix[i][kspec];
its++;
}
}
if (its > 0) xx /= its;
m_molNumSpecies_old[kspec] += xx;
m_molNumSpecies_old[kspec] = MAX(m_molNumSpecies_old[kspec], 1.0E-10);
/*
* If we are dealing with a deleted species, then
* we need to reinsert it into the active list.
*/
if (kspec >= m_numSpeciesRdc) {
vcs_reinsert_deleted(kspec);
m_molNumSpecies_old[m_numSpeciesRdc - 1] = xx;
vcs_elab();
goto L_CLEANUP;
}
vcs_elab();
}
}
}
if (vcs_elabcheck(0)) {
retn = 1;
goto L_CLEANUP;
}
for (i = 0; i < m_numElemConstraints; ++i) {
if (m_elType[i] == VCS_ELEM_TYPE_CHARGENEUTRALITY ||
(m_elType[i] == VCS_ELEM_TYPE_ABSPOS && m_elemAbundancesGoal[i] == 0.0)) {
for (kspec = 0; kspec < m_numSpeciesRdc; kspec++) {
if (m_elemAbundances[i] > 0.0) {
if (m_formulaMatrix[i][kspec] < 0.0) {
m_molNumSpecies_old[kspec] -= m_elemAbundances[i] / m_formulaMatrix[i][kspec] ;
if (m_molNumSpecies_old[kspec] < 0.0) {
m_molNumSpecies_old[kspec] = 0.0;
}
vcs_elab();
break;
}
}
if (m_elemAbundances[i] < 0.0) {
if (m_formulaMatrix[i][kspec] > 0.0) {
m_molNumSpecies_old[kspec] -= m_elemAbundances[i] / m_formulaMatrix[i][kspec];
if (m_molNumSpecies_old[kspec] < 0.0) {
m_molNumSpecies_old[kspec] = 0.0;
}
vcs_elab();
break;
}
}
}
}
}
if (vcs_elabcheck(1)) {
retn = 1;
goto L_CLEANUP;
}
/*
* For electron charges element types, we try positive deltas
* in the species concentrations to match the desired
* electron charge exactly.
*/
for (i = 0; i < m_numElemConstraints; ++i) {
double dev = m_elemAbundancesGoal[i] - m_elemAbundances[i];
if (m_elType[i] == VCS_ELEM_TYPE_ELECTRONCHARGE && (fabs(dev) > 1.0E-300)) {
bool useZeroed = true;
for (kspec = 0; kspec < m_numSpeciesRdc; kspec++) {
if (dev < 0.0) {
if (m_formulaMatrix[i][kspec] < 0.0) {
if (m_molNumSpecies_old[kspec] > 0.0) {
useZeroed = false;
}
}
} else {
if (m_formulaMatrix[i][kspec] > 0.0) {
if (m_molNumSpecies_old[kspec] > 0.0) {
useZeroed = false;
}
}
}
}
for (kspec = 0; kspec < m_numSpeciesRdc; kspec++) {
if (m_molNumSpecies_old[kspec] > 0.0 || useZeroed) {
if (dev < 0.0) {
if (m_formulaMatrix[i][kspec] < 0.0) {
double delta = dev / m_formulaMatrix[i][kspec] ;
m_molNumSpecies_old[kspec] += delta;
if (m_molNumSpecies_old[kspec] < 0.0) {
m_molNumSpecies_old[kspec] = 0.0;
}
vcs_elab();
break;
}
}
if (dev > 0.0) {
if (m_formulaMatrix[i][kspec] > 0.0) {
double delta = dev / m_formulaMatrix[i][kspec] ;
m_molNumSpecies_old[kspec] += delta;
if (m_molNumSpecies_old[kspec] < 0.0) {
m_molNumSpecies_old[kspec] = 0.0;
}
vcs_elab();
break;
}
}
}
}
}
}
if (vcs_elabcheck(1)) {
retn = 1;
goto L_CLEANUP;
}
L_CLEANUP: ;
vcs_tmoles();
#ifdef DEBUG_MODE
l2after = 0.0;
for (i = 0; i < m_numElemConstraints; ++i) {
l2after += SQUARE(m_elemAbundances[i] - m_elemAbundancesGoal[i]);
}
l2after = sqrt(l2after/m_numElemConstraints);
if (m_debug_print_lvl >= 2) {
plogf(" --- Elem_Abund: Correct Initial "
" Final\n");
for (i = 0; i < m_numElemConstraints; ++i) {
plogf(" --- "); plogf("%-2.2s", m_elementName[i].c_str());
plogf(" %20.12E %20.12E %20.12E\n", m_elemAbundancesGoal[i], ga_save[i], m_elemAbundances[i]);
}
plogf(" --- Diff_Norm: %20.12E %20.12E\n",
l2before, l2after);
}
#endif
return retn;
}
}